Process for preparing catalysts and catalyst compositions

Abstract

Disclosed are support-activators and catalyst compositions comprising the support-activators for polymerizing olefins in which the support-activator includes clay heteroadduct, prepare from a colloidal phyllosilicate such as a colloidal smectite clay, which is chemically-modified with a heterocoagulation agent. By limiting the amount of heterocoagulation reagent relative to the colloidal smectite clay as described herein, the smectite heteroadduct support-activator is a porous and amorphous solid which can be readily isolated from the resulting slurry by a conventional filtration process, and which can activate metallocenes and related catalysts toward olefin polymerization. Related compositions and processes are disclosed.

We claim: 
     
       1. A catalyst composition for olefin polymerization, the catalyst composition comprising:
 (a) at least one support-activator comprising a calcined smectite heteroadduct, the smectite heteroadduct comprising the contact product in a liquid carrier of [1] a colloidal smectite clay and [2] a heterocoagulation reagent comprising at least one cationic polymetallate and in an amount sufficient to provide a slurry of the smectite heteroadduct having a zeta potential in a range of from about positive (+)25 mV (millivolts) to about negative (−)25 mV, as quantified from the Electrokinetic Sonic Amplitude (ESA) Effect; and 
 (b) at least one metallocene compound having the formula
   (X 1 )(X 2 )(X 3 )(X 4 )M, wherein: 
 (i) M is zirconium or hafnium; 
 (ii) X 1  is a substituted or unsubstituted indenyl, fluorenyl, or cyclopentadienyl wherein any substituent is selected independently from a C 1 -C 20  hydrocarbyl, a C 1 -C 20  heterohydrocarbyl, or a fused C 4 -C 12  carbocyclic moiety; 
 (iii) X 2  is a substituted or unsubstituted indenyl or cyclopentadienyl, wherein any substituent is selected independently from a C 1 -C 20  hydrocarbyl or a C 1 -C 20  heterohydrocarbyl; 
 (iv) X 3  and X 4  are selected independently from a halide, a C 1 -C 20  hydrocarbyl, a C 1 -C 20  heterohydrocarbyl, or a C 1 -C 20  organoheteryl; and 
 (v) X 1  and X 2  are optionally bridged by a linking substituent >EX 5   2 , wherein E is selected from C or Si, and each X 5  is selected independently from a C 1 -C 20  hydrocarbyl. 
 
 
     
     
       2. The catalyst composition according to  claim 1 , wherein:
 (a) X 1  and X 2  are independently a substituted or an unsubstituted indenyl; and 
 (b) X 1  and X 2  are bridged by a linker substituent >EX 5   2 . 
 
     
     
       3. The catalyst composition according to  claim 1 , wherein:
 (a) X 1  and X 2  are independently a substituted or an unsubstituted indenyl; and 
 (b) X 1  and X 2  are unbridged. 
 
     
     
       4. The catalyst composition according to  claim 1 , wherein:
 (a) X 1  is a substituted or an unsubstituted fluorenyl; 
 (b) X 2  is a substituted cyclopentadienyl; and 
 (c) X 1  and X 2  are bridged by a linker substituent >EX 5   2 . 
 
     
     
       5. The catalyst composition according to  claim 1 , wherein:
 (a) X 1  is a substituted or an unsubstituted indenyl; 
 (b) X 2  is a substituted or an unsubstituted cyclopentadienyl; and 
 (c) X 1  and X 2  are bridged by a linker substituent >EX 5   2 . 
 
     
     
       6. The catalyst composition according to  claim 1 , wherein:
 (a) X 1  and X 2  are independently a substituted cyclopentadienyl; and 
 (b) X 1  and X 2  are unbridged. 
 
     
     
       7. The catalyst composition according to  claim 1 , wherein the linker substituent >EX 5   2  is present, and X 5  in each occurrence is selected independently from a C 1 -C 12  alkyl group, or C 2 -C 12  alkenyl group, or a C 6 -C 12  aromatic group. 
     
     
       8. The catalyst composition according to  claim 1 , wherein any substituent on X 1  and X 2  is selected independently from a C 1 -C 12  alkyl group, a C 2 -C 12  alkenyl group, a C 6 -C 12  aromatic group, a C 4 -C 12  heteroaromatic group, or a C 1 -C 15  organosilyl group. 
     
     
       9. The catalyst composition according to  claim 1 , wherein at least one of X 1 , X 2 , or the E atom of the linking substituent >EX 5   2 , when present, is substituted with a C 3 -C 12  olefinic group having the formula —(CH 2 ) n CH═CH 2 , wherein n is from 1-10. 
     
     
       10. The catalyst composition according to  claim 1 , wherein the metallocene compound comprises, bis(1,2,3-trimethylcyclopentadienyl)zirconium dichloride, bis(1,2,4-trimethylcyclopentadienyl)zirconium dichloride, bis-(1,2,3,4-tetramethylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(1,3-diethylcyclopentadienyl)-zirconium dichloride, bis(indenyl)zirconium dichloride, bis(4-methyl-1-indenyl)zirconium dichloride, bis(5-methyl-1-indenyl)zirconium)zirconium dichloride, bis(6-methyl-1-indenyl)zirconium dichloride, bis(7-methyl-1-indenyl)zirconium dichloride, bis(5-methoxy-1-indenyl)-zirconium dichloride, bis(2,3-dimethyl-1-indenyl)zirconium dichloride, bis(4,7-dimethyl-1-indenyl)zirconium dichloride, bis(4,7-dimethoxy-1-indenyl)zirconium dichloride, (indenyl)(fluorenyl)zirconium dichloride, bis(trimethylsilylcyclopentadienyl)zirconium dichloride, (cyclopentadienyl)(dimethylcyclopentadienyl)zirconium dichloride, (cyclopentadienyl)(trimethylcyclopentadienyl)zirconium dichloride, (cyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dichloride, (cyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dichloride, (cyclopentadienyl)(ethylcyclopentadienyl)zirconium dichloride, (cyclopentadienyl)(diethylcyclopentadienyl)zirconium dichloride, (cyclopentadienyl)(triethylcyclopentadienyl)zirconium dichloride, (cyclopentadienyl)(tetraethylcyclopentadienyl)zirconium dichloride, (cyclopentadienyl)(pentaethylcyclopentadienyl)-zirconium dichloride, (cyclopentadienyl)(2,7-di-t-butylfluorenyl)-zirconium dichloride, (cyclopentadienyl)(octahydrofluorenyl)zirconium dichloride, (methylcyclopentadienyl)-(t-butylcyclopentadienyl)zirconium dichloride, (methylcyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, (methylcyclopentadienyl)(octahydrofluorenyl)zirconium dichloride, (dimethylcyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, (dimethylcyclopentadienyl)(octahydrofluorenyl)zirconium dichloride, (ethylcyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, (ethylcyclopentadienyl)(octahydrofluorenyl)zirconium dichloride, (diethylcyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, (diethylcyclopentadienyl)(octahydrofluorenyl)-zirconium dichloride, bis(1-butyl-3-methylcyclopentadienyl) zirconium dichloride, rac-dimethylsilylene bis(2-methyl-4-phenylindenyl)zirconium dichloride, or any combination thereof. 
     
     
       11. The catalyst composition according to  claim 1 , wherein the catalyst composition further comprises:
 (c) at least one co-catalyst comprising an alkylating agent, a hydriding agent, or a silylating agent. 
 
     
     
       12. The catalyst composition according to  claim 11 , wherein the co-catalyst comprises trimethylaluminum, triethylaluminum (TEA), tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, ethyl-(3-alkylcyclopentadiyl)aluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, triisobutylaluminum (TIBAL), diethylaluminum chloride, ethyl-(3-alkylcyclopentadiyl)aluminum, or any combination thereof. 
     
     
       13. The catalyst composition according to  claim 1 , wherein:
 the smectite clay comprises montmorillonite, sauconite, nontronite, hectorite, beidellite, saponite, bentonite, or any combination thereof, and 
 the smectite clay is optionally monocation exchanged with at least one of lithium, sodium, or potassium. 
 
     
     
       14. The catalyst composition according to  claim 1 , wherein the cationic polymetallate comprises linear, cyclic or cluster aluminum compounds containing from 2-30 aluminum atoms. 
     
     
       15. The catalyst composition according to  claim 1 , wherein the cationic polymetallate comprises polyaluminum chloride, aluminum chlorhydrate, aluminum sesquichlorohydrate, or polyaluminum oxyhydroxychloride. 
     
     
       16. The catalyst composition according to  claim 15 , wherein the ratio of millimoles (mmol) of aluminum (Al) in the polyaluminum chloride, aluminum chlorhydrate, aluminum sesquichlorohydrate, or polyaluminum oxyhydroxychloride to grams (g) of colloidal smectite clay is in a range of from about 0.2 mmol Al/g clay to about 2.5 mmol Al/g clay. 
     
     
       17. The catalyst composition according to  claim 15 , wherein the ratio of millimoles (mmol) of aluminum (Al) in the polyaluminum chloride, aluminum chlorhydrate, aluminum sesquichlorohydrate, or polyaluminum oxyhydroxychloride to grams (g) of colloidal smectite clay is in a range of from about 0.5 mmol Al/g clay to about 2.2 mmol Al/g clay. 
     
     
       18. The catalyst composition according to  claim 1 , wherein the cationic polymetallate comprises a first metal oxide which is chemically-treated with a second metal oxide, a metal halide, a metal oxyhalide, or a combination thereof, in an amount sufficient to provide a colloidal suspension of the chemically-treated first metal oxide having a zeta potential of greater than positive 20 mV (millivolts). 
     
     
       19. The catalyst composition according to  claim 1 , wherein the cationic polymetallate comprises fumed silica, fumed alumina, fumed silica-alumina, fumed magnesia, fumed zinc oxide, fumed titania, fumed zirconia, fumed ceria, or any combination thereof, which is chemically-treated with polyaluminum chloride, aluminum chlorhydrate, aluminum sesquichlorohydrate, polyaluminum oxyhydroxychloride, or any combination thereof. 
     
     
       20. The catalyst composition according to  claim 1 , wherein the cationic polymetallate comprises aluminum chlorhydrate-treated fumed silica, aluminum chlorhydrate-treated fumed alumina, aluminum chlorhydrate-treated fumed silica-alumina, or any combination thereof. 
     
     
       21. The catalyst composition according to  claim 1 , wherein the liquid carrier comprises water. 
     
     
       22. The catalyst composition according to  claim 21 , wherein the liquid carrier further comprises a surfactant selected from an anionic surfactant, a cationic surfactant, a non-ionic surfactant, or an amphoteric surfactant. 
     
     
       23. The catalyst composition according to  claim 22 , wherein the cationic surfactant is selected from:
 a primary amine, a secondary amine, or a tertiary amine; or 
 a primary ammonium chloride or bromide, a secondary ammonium chloride or bromide, a tertiary ammonium chloride or bromide, or a quaternary ammonium chloride or bromide. 
 
     
     
       24. The catalyst composition according to  claim 22 , wherein the non-ionic surfactant is selected from an ethoxylate, a glycol ether, a fatty alcohol polyglycol ether, or a combination thereof. 
     
     
       25. The catalyst composition according to  claim 1 , wherein the colloidal smectite clay and the heterocoagulation reagent are contacted in an amount sufficient to provide a slurry of a smectite heteroadduct having a zeta potential in a range of from about positive (+)20 mV (millivolts) to about negative (−)20 mV. 
     
     
       26. The catalyst composition according to  claim 1 , wherein the colloidal smectite clay and the heterocoagulation reagent are contacted in an amount sufficient to provide a slurry of a smectite heteroadduct having a zeta potential in a range of from about positive (+)15 mV (millivolts) to about negative (−)15 mV. 
     
     
       27. A process for polymerizing olefins comprising contacting at least one olefin monomer and the catalyst composition according to  claim 1  under polymerization conditions to form a polyolefin. 
     
     
       28. The process for polymerizing olefins according to  claim 27 , wherein the at least one olefin monomer is selected from [a] ethylene or propylene, or [b] ethylene in combination with at least one comonomer selected from propylene, 1-butene, 2-butene, 3-methyl-1-butene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 3-ethyl-1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1,3-butadiene, isoprene, piperylene, 2,3-dimethyl-1,3-butadiene, 1,4-pentadiene, 1,7-hexadiene, vinylcyclohexane, or any combination thereof. 
     
     
       29. The process for polymerizing olefins according to  claim 27 , wherein the process comprises polymerization in a gas phase reactor, a slurry loop, dual slurry loops in series, multiple slurry tanks in series, a slurry loop combined with a gas phase reactor, a continuous stirred reactor in a batch process, or combinations thereof. 
     
     
       30. A method of making an olefin polymerization catalyst composition, the method comprising contacting in any order:
 (a) at least one support-activator comprising a calcined smectite heteroadduct, the smectite heteroadduct comprising the contact product in a liquid carrier of [1] a colloidal smectite clay and [2] a heterocoagulation reagent comprising at least one cationic polymetallate and in an amount sufficient to provide a slurry of the smectite heteroadduct having a zeta potential in a range of from about positive (+)25 mV (millivolts) to about negative (−)25 mV, as quantified from the Electrokinetic Sonic Amplitude (ESA) Effect; and 
 (b) at least one metallocene compound having the formula
   (X 1 )(X 2 )(X 3 )(X 4 )M, wherein: 
 (i) M is zirconium or hafnium; 
 (ii) X 1  is a substituted or unsubstituted indenyl, fluorenyl, or cyclopentadienyl wherein any substituent is selected independently from a C 1 -C 20  hydrocarbyl, a C 1 -C 20  heterohydrocarbyl, or a fused C 4 -C 12  carbocyclic moiety; 
 (iii) X 2  is a substituted or unsubstituted indenyl or cyclopentadienyl, wherein any substituent is selected independently from a C 1 -C 20  hydrocarbyl or a C 1 -C 20  heterohydrocarbyl; 
 (iv) X 3  and X 4  are selected independently from a halide, a C 1 -C 20  hydrocarbyl, a C 1 -C 20  heterohydrocarbyl, or a C 1 -C 20  organoheteryl; and 
 (v) X 1  and X 2  are optionally bridged by a linking substituent >EX 5   2 , wherein E is selected from C or Si, and each X 5  is selected independently from a C 1 -C 20  hydrocarbyl. 
 
 
     
     
       31. The method of making an olefin polymerization catalyst composition according to  claim 30 , the method further comprising contacting in any order:
 (c) at least one co-catalyst comprising an alkylating agent, a hydriding agent, or a silylating agent.